Nitrophenyl-sulfonyl-imidazoles and use thereof for controlling vegetable and animal pests

ABSTRACT

Novel nitrophenyl-sulphonyl-imidazoles of the formula  
                 
 
     in which  
     X, R 1 , R 2  and R 3  have the meanings stated in the description, a process for the preparation of novel substances and their use for controlling vegetable and animal pests.

[0001] The present invention relates to novelnitrophenyl-sulphonyl-imidazoles, a process for their preparation andtheir use for controlling vegetable and animal pests.

[0002] It has already become known that specificphenylsultphonyl-imidazoles and phenyl-sulphonyl-benzimidazoles havefungicidal properties (cf. EP-A 0 238 824 and WO 97-06 171). Thus,1-(2-methyl-5-nitro-phenylsulphonyl)-benzotriazole,2-methyl-1-(2-methyl-5-nitro-phenylsulphonyl)-imidazole and1-(2-methyl-5-nitro-phenylsulphonyl)-2-chloro-6,6-difluoro-[1,3]-dioxolo-[4,5-f]-benzinidazolecan be used for controlling fungi. The activity of these substances isgood but is unsatisfactory in some cases at low application rates.

[0003] Novel nitrophenyl-sulphonyl-imidazoles of the formula

[0004] in which

[0005] a) X represents cyano,

[0006] R¹ represents halogen, alkyl, or phenyl,

[0007] R² represents halogen, alkyl or phenyl or

[0008] R¹ and R², together with the carbon atoms to which they arebonded, represent an optionally substituted benzene ring or represent anoptionally substituted heterocyclic ring and

[0009] R³ represents halogen, alkyl or phenyl or

[0010] b) X represents halogen,

[0011] R¹ represents halogen, alkyl or phenyl,

[0012] R² represents halogen, alkyl or phenyl or

[0013] R¹ and R², together with the carbon atoms to which they arebonded, represent an optionally substituted heterocyclic ring or

[0014] R¹ and R², together represent a doubly bonded radical of theformula

[0015]  and

[0016] R³ represents halogen, alkyl or phenyl, have now been found.

[0017] It has furthermore been found thatnitrophenyl-sulphonyl-imidazoles of the formula (I) are obtained ifimidazole derivatives of the formula

[0018] in which

[0019] R¹, R² and X have the abovementioned meanings,

[0020] are reacted with nitrobenzene-sulphonyl halides of the formula

[0021]  in which

[0022] R³ has the abovementioned meaning and

[0023] Hal represents chlorine or bromine,

[0024] optionally in the presence of an acid acceptor and optionally inthe presence of a diluent.

[0025] Finally, it has been found that thenitrophenyl-sulphonyl-imidazoles of the formula (I) are very suitablefor controlling vegetable and animal pests in crop protection and inmaterial protection.

[0026] Surprisingly, the substances according to the invention exhibit abetter fungicidal activity than1-(2-methyl-5-nitro-phenylsulphonyl)-benzotriazole and2-methyl-1-(2-methyl-5-nitro-phenylsulphonyl)-imidazole, which areconstitutionally similar, previously known active substances having thesame type of activity.

[0027] The substances according to the invention are generally definedby the formula (I).

[0028] A preferred group of substances according to the invention arenitrophenyl-sulphonyl-imidazoles of the formula

[0029] Here, the substituents preferably have the meanings stated below.

[0030] R¹ preferably represents fluorine, chlorine, bromine,straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl.

[0031] R² preferably represents fluorine, chlorine, bromine,straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl.

[0032] R¹ and R², together with the carbon atoms to which they arebonded, furthermore preferably represent a benzene ring which can bemonosubstituted to trisubstituted, identically or differently, by

[0033] halogen, cyano, nitro, formyl, carbamoyl, thiocarbamoyl;

[0034] alkyl, alkoxy, alkylthio or alkylsulphonyl, each having 1 to 5carbon atoms;

[0035] halogenoalkyl, halogenoalkoxy, halogenoalkylthio orhalogenoalkylsulphonyl, each having 1 to 4 carbon atoms and 1 to 5identical or different halogen atoms;

[0036] halogenoalkenyl or halogenoalkenyloxy, each of which isstraight-chain or branched and each of which has 2 to 4 carbon atoms and1 to 5 identical or different halogen atoms;

[0037] alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl,alkylsulphonyloxy, hydroximinoalkyl, alkoximinoalkyl orcyanoimino(alkoxy)alkyl, each having 1 to 4 carbon atoms in theindividual alkyl moieties;

[0038] cycloalkyl having 3 to 6 carbon atoms;

[0039] phenyl, phenoxy, phenylthio, pyridyl, pyridyloxy and/orpyridylthio, it being possible for each of these radicals to bemonosubstituted or disubstituted, identically or differently, byhalogen, cyano, nitro, alkyl having 1 to 4 carbon atoms and/orhalogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical ordifferent halogen atoms.

[0040] R¹ and R², together with the carbon atoms to which they arebonded, furthermore preferably represent a benzene ring which issubstituted by doubly linked alkylene having 3 or 4 carbon atoms ordioxyalkylene having 1 or 2 carbon atoms, it being possible for thealkylene or dioxyalkylene groups to be monosubstituted totetrasubstituted, identically or differently, by halogen, alkyl having 1to 4 carbon atoms and/or halogenoalkyl having 1 or 2 carbon atoms and 1to 5 identical or different halogen atoms.

[0041] R¹ and R², together with the carbon atoms to which they arebonded, furthermore preferably represent a 5- or 6-membered heterocyclicring which contains one, two or three identical or differentheteroatoms, such as oxygen, sulphur and/or nitrogen, and may bemonosubstituted to trisubstituted, identically or differently, byhalogen, cyano, nitro, hydroxyl, amino, formyl, carboxyl, carbarnoyl,thiocarbamoyl, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 to 4carbon atoms and 1 to 5 identical or different halogen atoms,alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,cycloalkyl having 3 to 6 carbon atoms, halogenoalkylsulphinyl having 1to 4 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5 identicalor different halogen atoms, alkylamino having 1 to 4 carbon atoms,hydroxyalkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4carbon atoms in each alkyl group, alkylcarbonyl having 1 to 4 carbonatoms in the alkyl moiety, hydroximinoalkyl having 1 to 4 carbon atomsin the alkyl moiety, alkoximinoalkyl having 1 to 4 carbon atoms in thealkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety,alkylcarbonyloxy having 1 to 4 carbon atoms in the alkyl moiety and/orhalogenoalkylcarbonyloxy having 1 to 4 carbon atoms in the halogenoalkylgroup and 1 to 5 identical or different halogen atoms, the oxygen atomsnot being adjacent where the heterocyclic ring contains more than oneoxygen atom.

[0042] R³ preferably represents fluorine, chlorine, bromine,straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl.

[0043] A further group of preferred substances according to theinvention are nitrophenyl-sulphonyl-imidazoles of the formula

[0044] In this formula, the substituents preferably have the meaningsstated below.

[0045] Hal¹ preferably represents fluorine, chlorine or bromine.

[0046] R¹ preferably represents fluorine, chlorine, bromine,straight-chain or branched atkyl having 1 to 6 carbon atoms or phenyl.

[0047] R² preferably represents fluorine, chlorine, bromine,straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl.

[0048] R¹ and R², together with the carbon atoms to which they arebonded, furthermnore preferably represent a 5- or 6-memberedheterocyclic ring which contains one, two or three identical ordifferent heteroatoms, such as oxygen, sulphur and/or nitrogen, and maybe monosubstituted to trisubstituted, identically or differently, byhalogen, cyano, nitro, hydroxyl, amino, formyl, carboxyl, carbamoyl,thiocarbamoyl, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 to 4carbon atoms and 1 to 5 identical or different halogen atoms,alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,cycloalkyl having 3 to 6 carbon atoms, hialogenoalkylsulphinyl having 1to 4 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5 identicalor different halogen atoms, alkylamino having 1 to 4 carbon atoms,hydroxyalkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4carbon atoms in each alkyl group, alkylcarbonyl having 1 to 4 carbonatoms in the alkyl moiety, hydroximinoalkyl having 1 to 4 carbon atomsin the alkyl moiety, alkoximinoalkyl having 1 to 4 carbon atoms in thealkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety,alkylcarbonyloxy having 1 to 4 carbon atoms in the alkyl moiety and/orhalogenoalkylcarbonyloxy having 1 to 4 carbon atoms in the halogenoalkylgroup having 1 to 5 identical or different halogen atoms, the oxygenatoms not being adjacent where the heterocyclic ring contains more thanone oxygen atom

[0049] R¹ and R² together furthermore preferably represent a doublybonded radical of the formula

[0050] R³ preferably represents fluorine, chlorine, bromine,straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl.

[0051] Particularly preferred are compounds of the formula (Ia), inwhich

[0052] R¹ represents fluorine, chlorine, bromine, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl orphenyl,

[0053] R² represents fluorine, chlorine, bromine, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or phenylor

[0054] R¹ and R², together with the carbon atoms to which they arebonded, represent a benzene ring which may be monosubstituted totrisubstituted, identically or differently, by

[0055] fluorine, chlorine, bromine, cyano, nitro, forrnyl, methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- ori-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphonyl,ethylsulphonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy,trifluoromethoxy, difluorochloromethoxy, tri fluoroethoxy,difluoromethylthio, difluorochloromethylthio, trifluoromethylthio,trifluoromethylsulphonyl, acetyl, propionyl, acetyloxy, methoxycarbonyl,ethoxycarbonyl, butoxycarbonyl, methylsulphonyloxy, ethylsulphonyloxy,hydroximinomethyl, hydroximinoethyl, methoximinomethyl,ethoximinomethyl, methoximinomethyl, ethoximinoethyl,cyanoimino(methoxy)methyl,

[0056] cyclopropyl, cyclopentyl, cyclohexyl or

[0057] phenyl, phenoxy, phenylthio, pyridyl, pyridyloxy and/orpyridylthio, it being possible for each of these radicals to bemonosubstituted or disubstituted, identically or differently, byfluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, trifluoromethyl,trichloromethyl and/or difluoromethyl, or

[0058] R¹ and R², together with the carbon atoms to which they arebonded, represent a benzene ring which is substituted bypropane-1,3-diyl, butane-1,4-diyl, methylenedioxy or ethylenedioxy, eachof which is doubly linked, it being possible for the alkylene ordioxyalkylene groups to be monosubstituted to tetrasubstituted,identically or differently, by fluorine, chlorine, trifluoromethyl,methyl, ethyl and/or n-propyl, or

[0059] R¹ and R², together with the carbon atoms to which they arebonded, represent a fused furan, thiophene, pyrrole, oxazole, thiazole,imidazole, isoxazole, isothiazole, pyrazole, 1,2,3-oxadiazole,1,2,3-thiadiazole, 1,2,3-triazole, pyridine, pyridazine, pyrazine,pyrimidine or 1,2,4-triazine ring, it being possible for these radicalsto be monosubstituted or disubstituted, identically or differently, byfluorine, chlorine, bromine, cyano, nitro, amino, hydroxyl, formyl,carboxyl, carbamoyl, thiocarbomyl, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio,ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl, ethylsulphonyl, trifluoromethyl, difluoromethoxy,trifluoromethoxy, difluoromethylthio, trifluoromethylthio,trifluoromethylsulphinyl or trifluoromethylsulphonyl, methylamino,ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl,propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl,methylsulphonyloxy, ethylsulphonyloxy, hydroxyiminomethyl,hydroxyiminoethyl, methoxyiminomethyl, ethoxyiminomethyl,methoxyiminoethyl and/or ethoxyiminoethyl and

[0060] R³ represents fluorine, chlorine, bromine, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl orphenyl.

[0061] Particularly preferred in addition are compounds of the formula(Ib), in which

[0062] Hal¹ represents fluorine, chlorine or bromine,

[0063] R¹ represents fluorine, chlorine, bromine, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl orphenyl,

[0064] R² represents fluorine, chlorine, bromine, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl orphenyl, or

[0065] R¹ and R², together with the carbon atoms to which they arebonded, represent a fused furan, thiophene, pyrrole, oxazole, thiazole,imidazole, isoxazole, isothiazole, pyrazole, 1,2,3-oxadiazole,1,2,3-thiadiazole, 1,2,3-triazole, pyridine, pyridazine, pyrazine,pyrimidine or 1,2,4-triazine ring, it being possible for these radicalsto be monosubstituted or disubstituted, identically or differently, byfluorine, chlorine, bromine, cyano, nitro, amino, hydroxyl, formyl,carboxyl, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio,ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl, ethylsulphonyl, trifluoromethyl, difluoromethoxy,trifluoromethoxy, difluoromethylthio, trifluoromethylthio,trifluoromethylsulphinyl or trifluoromethylsulphonyl, methylamino,ethylamino, n- or i-propylamino, dimethylarnino, diethylamino, acetyl,propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl,methylsulphonyloxy, ethylsulphonyloxy, hydroxyiminomethyl,hydroxyiminoethyl, methoxyiminomethyl, ethoxyiminomethyl,methoxyiminoethyl and/or ethoxyiminoethyl, or

[0066] R¹ and R² together represent a doubly bonded radical of theformula

[0067]  and

[0068] R³ represents fluorine, chlorine, bromine, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl orphenyl.

[0069] The abovementioned meanings of the substituents can be combinedwith one another in any desired manner. In addition, individualdefinitions may also be omitted.

[0070] The nitrophenyl-sulphonylimidazoles shown in the following tablesmay be mentioned as examples of substances according to the invention.TABLE 1 (Ic)

R¹ R² R³ X Cl Cl —CH₃ Cl Cl Cl —CH₃ Br —C₂H₅ Cl —CH₃ Cl —C₂H₅ Br —CH₃ Br—C₃H₇-n Cl —CH₃ Cl —CH₃ F —CH₃ —CN —CH₃

—CH₃ Br Br Br —C₂H₅ Br Br Br —C₃H₇-n Cl Br Br

Cl Br Br F Cl Cl Cl Cl —CN CH₃ Br C₂H₅ Cl CH₃ Br —C₃H₇-n Cl CH₃ Br

Br

[0071] TABLE 2 (Id)

R³ = C₂H₅ C₃H₇

F Cl

[0072] TABLE 3 (Ie)

[0073] wherein

[0074] R³ represents the substituents mentioned in Table 2. TABLE 4 (If)

R³ X —C₂H₅ Cl —C₂H₅ Br —C₂H₅ —CN —C₃H₇ Cl —C₃H₇-n Br —C₃H₇-n —CN

Cl

Br

—CN F Cl F Br F —CN Cl Cl Cl Br Cl —CN

[0075] TABLE 5 (Ig)

[0076] where

[0077] R³ represents the substituents mentioned in Table 2. TABLE 6 (Ih)

=

[0078] TABLE 7 (Ii)

Hal¹

Cl

Cl

Cl

Br

Br

Br

[0079] If 2,5-dibromo-4-methyl-1H-imidazole and2-methyl-5-nitrobenzenesulphonyl chloride are used as startingmaterials, the course of the process according to the invention can beillustrated by the following equation.

[0080] The imidazole derivatives required as starting materials forcarrying out the process according to the invention are generallydefined by the formula (II). In this formula, R¹, R² and X preferablyhave those meanings which have already been mentioned in connection withthe description of the substances, according to the invention, offormula (I) as being preferred for the substituents.

[0081] The compounds of the formula (II) may be present in the followingtwo tautomeric forms.

[0082] If the molecular unit

[0083] is symmetrical, the tautomeric forms are identical. In thereaction, according to the invention, with nitrobenzenesulphonyl halidesof the formula (III), only one specific end product of the formula (I)is thus formed in each case, and is formed independently of which of thetwo tautomeric forms reacts.

[0084] If the molecular unit

[0085] is asymmetrical, the two tautomeric forms are not identical. Inthe reaction, according to the invention, with nitrobenzene-sulphonylhalides of the formula (III), end products of the formula (I) which arederived from the tautomeric forms of the formulae (IIa) and/or (IIb) canthus form. If both tautomers react, end products of the formula (I) areobtained in the form of mixtures.

[0086] The imidazole derivatives of the formula (II) are known or can beprepared by known methods (cf. WO 97-06171, Chem. Ber. 85, (1952)1012-1020), J. Med. Chem. 34 (1991), 1110-1116 and J. Chem. Soc. 1965,3017-3021).

[0087] The nitrobenzene-sulphonyl halides furthermore required asstarting materials for carrying out the process according to theinvention are generally defined by the formula (III). In this formula,R³ preferably has those meanings which have already been mentioned inconnection with the description of the substances, according to theinvention, of the formula (I) as being preferred for these substituents.Hal also preferably represents chlorine or bromine.

[0088] The nitrobenzene-sulphonyl halides of the formula (III) are knownor can be prepared by known methods (cf. EP-A 0 238 824).

[0089] All customary inorganic or organic bases are suitable as acidacceptors for carrying out the process according to the invention.Alkaline earth metal or alkali metal hydrides, hydroxides, amides,alcoholates, acetates, carbonates or bicarbonates, such as, for example,sodium hydride, sodium amide, sodium methylate, sodium ethylate,potassium tert-butylate, sodium hydroxide, potassium hydroxide, sodiumacetate, potassium acetate, calcium acetate, sodium carbonate, potassiumcarbonate, potassium bicarbonate or sodium bicarbonate, furthermoreammonium compounds, such as ammonium hydroxide, ammonium acetate orammonium carbonate, and tertiary amines, such as trimethylanine,triethylamine, tributylamine, N,N-dimethylanilinie,N,N-dimethyl-benzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazobicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU), maypreferably be used.

[0090] All inert organic solvents are suitable as diluents for carryingout the process according to the invention. Aliphatic, alicyclic oraromatic hydrocarbons such as, for example, petroleum ether, hexane,heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene ordecalin; halogenated hydrocarbons, such as, for example, chlorobenzene,dichlorobenzene, dichloromethane, chloroform, tetrachloromethane,dichloroethane or trichloroethane; ethers such as diethyl ether,diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole;ketones, such as acetone, butanone, methyl isobutyl ketone orcyclohexanone; nitriles, such as acetonitrile, propionitrile, n- ori-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethyl-phosphorotriamide; esters, such as methyl acetate or ethylacetate; sulphoxides, such as dimethyl sulphoxide; sulphones, such assulpholane, or amines, such as pyridine, may preferably be used.

[0091] When carrying out the process according to the invention, thereaction temperatures can be varied within a relatively large range. Ingeneral, temperatures betwen 0° C. and 150° C., preferably temperaturesbetween 10° C. and 120° C., are employed.

[0092] The process according to the invention is generally carried outunder atmospheric pressure. However, it is also possible to employsuperatmospheric or reduced pressure.

[0093] When the process according to the invention is carried out, ingeneral 1 to 1.5 mol of nitrobenzene-sulphonyl halide of the formula(III) and an equivalent amount or an excess of acid acceptor are usedper 1 mol of imidazole derivative of the formula (II). The working up iseffected by customary methods. In general, water is added to thereaction mixture, the mixture formed is extracted several times with anorganic solvent slightly soluble in water, and the combined organicphases are dried and evaporated down. The substances obtained canoptionally be purified by customary methods, such as chromatography orrecrystallization.

[0094] The active substances according to the invention are suitable forcontrolling vegetable pests and can therefore be used for controllingundesired microorganisms, such as fungi or bacteria, in crop protectionand in material protection.

[0095] Fungicides can be used in crop protection for controllingplasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes, Deuteromycetes.

[0096] Bactericides can be used used in crop protection for controllingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

[0097] Some pathogens of fungal and bacterial diseases which areincluded under the general terms listed above may be mentioned by way ofexample without imposing any limitation:

[0098] Xanthomonas species, such as Xanthomonas campestris pv. oryzae;

[0099] Pseudomonas species, such as Pseudomonas syringae pv. lachrymans;

[0100] Erwinia species, such as Erwinia amylovora;

[0101] Pythium species, such as Pythium ultimum;

[0102] Phytophthora species, such as Phytophthora infestans;

[0103] Pseudoperonospora species, such as Pseudoperonospora humuli orPseudoperonospora cubensis;

[0104] Plasmopara species, such as Plasmopara viticola;

[0105] Bremia species, such as Bremia lactucae;

[0106] Peronospora species, such as Peronospora pisi or P. brassicae;

[0107] Erysiphe species, such as Erysiphe graminis;

[0108] Sphaerotheca species, such as Sphaerotheca fuliginea;

[0109] Podosphiaera species, such as, for example, Podosphaeraleucotriclia;

[0110] Venturia species, such as Venturia inaequalis;

[0111] Pyrenophora species, such as Pyrenophora teres or P. graminea(Conidia form: Drechslera, Syn: Helminthosporium);

[0112] Cochliobolus species, such as Cochliobolus sativus (Conidia form:Drechslera, Syn: Helminthosporium);

[0113] Uromyces species, such as Uromyces appendiculatus;

[0114] Puccinia species, such as Puccinia recondita;

[0115] Scierotinia species, such as Sclerotinia scierotiorum;

[0116] Tilletia species, such as Tilletia caries;

[0117] Ustilago species, such as Ustilago nuda or Ustilago avenae;

[0118] Pellicularia species, such as Pellicularia sasakii;

[0119] Pyricularia species, such as Pyricularia oryzae;

[0120] Fusarium species, such as Fusarium culmorum;

[0121] Botrytis species, such as Botrytis cinerea;

[0122] Septoria species, such as Septoria nodorum;

[0123] Leptosphaeria species, such as Leptosphaeria nodorum;

[0124] Cercospora species, such as Cercospora canescens;

[0125] Altemaria species, such as, for example, Alternaria brassicae;

[0126] Pseudocercosporella species, such as Pseudocercosporellaherpotrichoides.

[0127] The good plant tolerance of the active substances in theconcentrations required for controlling plant diseases permits thetreatment of above-ground plant parts, of plant material and seed and ofthe soil.

[0128] The active substances according to the invention can beparticularly successfully used for controlling diseases in viticulture,fruit cultivation and vegetable cultivation, such as against Venturia,Podosphaera, and Plasmopara species. Rice diseases, such as Pyriculariaspecies, are also successfully controlled.

[0129] In material protection, the substances according to the inventioncan be used for the protection of technical materials from attack anddestruction by undesired microorganisms.

[0130] In the present context, technical materials are to be understoodas meaning nonliving materials which have been prepared for use inindustry. For example, technical materials which are to be protected byactive substances according to the invention against microbial change ordestruction may be adhesives, glues, paper and cardboard, textiles,leather, wood, coating materials and plastics articles, coolinglubricants and other materials which may be attacked or decomposed bymicroorganisms. Parts of production plants, for example coolingcirculations, which may be impaired by multiplication of organisms mayalso be mentioned among the materials to be protected. In the presentinvention, preferably adhesives, glues, papers and cardboards, leather,wood, coating materials, cooling lubricants and heat-transfer liquidsmay be mentioned as technical materials, particularly preferably wood.

[0131] For example, microorganisms of the following genera may bementioned:

[0132] Altemaria, such as Altemaria tenuis,

[0133] Aspergillus, such as Aspergillus niger,

[0134] Chaetomium, such as Chaetomium globosum,

[0135] Coniophora, such as Coniophora puetana,

[0136] Lentinus, such as Lentinus tigrinus,

[0137] Penicillium, such as Penicillium versicolor,

[0138] Aureobasidium, such as Aureobasidium pullulans,

[0139] Scierophoma, such as Sclerophoma pityophila,

[0140] Trichodenna, such as Trichoderma viride,

[0141] Escherichia, such as Escherichia coli,

[0142] Pseudomonas, such as Pseudomonas aeruginosa,

[0143] Staphylococcus, such as Staphylococcus aureus.

[0144] The active substances according to the invention which have goodplant tolerance and advantageous toxicity with respect to warm-bloodedanimals are also suitable for controlling animal pests, in particularinsects, arachnids and nematodes, which occur in agriculture, inforests, in horticulture, in the protection of stored goods andmaterials and in the hygiene sector or in the area of veterinarymedicine. The substances are effective against normally sensitive andresistant species and against pests in all or individual stages ofdevelopment. The abovementioned animal pests include:

[0145] From the order of the Isopoda, for example Oniscus asellus,Armadillidium vulgare, Porcellio scaber.

[0146] From the order of the Diplopoda, for example Blaniulusguttulatus.

[0147] From the order of the Chilopoda, for example Geophiluscarpophagus, Scutigera spec.

[0148] From the order of the Symphyla, for example Scutigerellaimmaculate.

[0149] From the order of the Thysanura, for example Lepisma saccharina.

[0150] From the order of the Collembola, for example Onychiurus armatus.

[0151] From the order of the Orthoptera, for example Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germnanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratonioides,Melanoplus differentialis, Schistocerca gregaria.

[0152] From the order of the Dernaptera, for example Forficulaauricularia.

[0153] From the order of the Isoptera, for example Reticulitermes spp.

[0154] From the order of the Anoplura, for example Pediculus humanuscorporis, Haematopinus spp., Linognathus spp.

[0155] From the order of the Mallophaga, for example Trichodectes spp.,Damalinea spp.

[0156] From the order of the Thysanoptera, for example Hercinothripsfemoralis, Thrips tabaci.

[0157] From the order of the Heteroptera, for example Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus, Triatoma spp.

[0158] From the order of the Homoptera, for example Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiplium avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

[0159] From the order of the Lepidoptera, for example Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Eanras insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Spodoptera litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima, Tortrix viridana.

[0160] From the order of the Coleoptera, for example Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica.

[0161] From the order of the Hymenoptera, for example Diprion spp.,Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

[0162] From the order of the Diptera, for example Aedes spp., Anophelesspp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp.,Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebraspp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa.

[0163] From the order of the Siphonaptera, for example Xenopsyllacheopis, Ceratophyllus spp.

[0164] From the order of the Arachnida, for example Scorpio maurus,Latrodectus mactans.

[0165] From the order of the Acarina, for example Acarus siro, Argasspp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis,Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Aiublyommaspp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp.,Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp.,Tetranychus spp.

[0166] The phytoparasitic nematodes include, for example, Pratylenchusspp., Radopholus similis, Ditylenchus dipsaci, Tylenchulussemipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp.,Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.

[0167] The substances which can be used according to the invention canbe particularly successfully employed for controlling plant-damagingmites, such as against the bean spider mite (Tetranychus urticae), orfor controlling plant-damaging insects, such as against the caterpillarsof the diamond-back moth (Plutella maculipennis), the larvae of thehorseradish leaf beetle (Phaedon cochleariae), and the green rice cicada(Nephotettix cincticeps).

[0168] The substances which may be used according to the invention actnot only against plant pests, hygiene pests and pests of stored goodsbut also in the veterinary medical sector against animal parasites(ectoparasites), such as scale ioxodid ticks, argasidae, mange mites,trombiidae, flies (biting and licking), parasitic fly larvae, lice,biting lice, bird lice and fleas. These parasites include:

[0169] From the order of the Anoplurida, for example Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

[0170] From the order of the Mallophagida and the suborders Amblycerinaand lschnocerina, for example Trimenopon spp., Menopon spp., Trinotonspp., Bovicola spp., Wemeckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

[0171] From the order of Diptera and the suborders Nematocerina andBraclhycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.

[0172] From the order of the Siphonapterida, for example Pulex spp.,Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

[0173] From the order of the Heteropterida, for example Cimex spp.,Triatoma spp., Rhodnius spp., Panstrongylus spp.

[0174] From the order of the Blattarida, for example Blatta orientalis,Periplaneta americana, Blattela germanica, Supella spp.

[0175] From the subclass of the Acaria (Acarida) and the orders of theMeta- and Mesostigmata, for example Argas spp., Omithodorus spp.,Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentorspp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dernanyssusspp., Raillietia spp., Pneumonyssus spp., Stemostoma spp., Varroa spp.

[0176] From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

[0177] The active substances according to the invention are alsosuitable for increasing the harvest yield. In addition, they have lowtoxicity and possess good plant tolerance.

[0178] Depending on their respective physical and/or chemicalproperties, the active substances can be converted into the customaryformulations, such as solutions, emulsions, suspensions, powders, foams,pastes, granules, aerosols, very finely encapsulated forms in polymericsubstances and in coating materials for seed and ULV cold and warn mistformulations.

[0179] These formulations are prepared in a known manner, for example bymixing the active substances with extenders, that is to say liquidsolvents, liquefied gases under pressure and/or solid carriers,optionally with the use of surfactants, that is to say emulsifiersand/or dispersants and/or form-producing compositions. In the case ofthe use of water as an extender, for example, organic solvents may alsobe used as auxiliary solvents. Suitable liquid solvents are essentially:aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, e.g. mineral oil fractions, alcohols such asbutanol or glycol, and their ethers and esters, ketones, such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, and water. Liquefied gaseous extenders or carriers are thoseliquids which are gaseous at normal temperature and under normalpressure, for example aerosol propellants, such as halogenohydrocarbonsand butane, propane, nitrogen and carbon dioxide. Suitable solidcarriers are: for example, crushed natural minerals, such as kaolins,aluminas, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and crushed synthetic minerals, such as finelydivided silica, alumina and silicates. Suitable solid carriers forgranules are: for example, crushed and fractionated natural minerals,such as calcite, marble, pumice, sepiolite, dolomite, and syntheticgranules of inorganic and organic powders and granules of organicmaterial, such as sawdust, coconut shells, maize cobs and tobacco stems.Suitable emulsifiers and/or form-producing compositions are: forexample, nonionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylarylpolyglycol ethers, alkylsulphonates, alkylsulplates, arylsulptionatesand protein hydrolysis products. Suitable dispersants are: for example,ligninsulphite waste liquors and methylcellulose.

[0180] Adherents, such as carboxyrnethylcellulose, natural and syntheticpulverulent, granular or latex-like polymers may be used in theformulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetateand natural phospholipids, such as kephalins and lecithins, andsynthetic phospholipids. Further additives may be mineral and vegetableoils.

[0181] Colorants, such as inorganic pigments, e.g. iron oxide, titaniumoxide, Prussian blue, and organic dyes, such as alizarin, azo and metalphthalocyanine dyes, and trace nutrients, such as salts of iron,manganese, boron, copper, cobalt, molybdenum and zinc, may be used.

[0182] The formulations contain in general between 0.1 and 95 percent byweight of active substance, preferably between 0.5 and 90%.

[0183] Depending on their respective physical and/or chemicalproperties, the active substances can be converted into the customaryformnulations, such as solutions, emulsions, suspensions, powders,foams, pastes, granules, aerosols, very finely encapsulated forms inpolymeric substances and in coating materials for seed, and ULV coldmist and warm mist formulations.

[0184] The active substances according to the invention can be used, assuch or in their formulations, also as a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, in order, forexample, to broaden the action spectrum or to prevent the development ofresistance. In many cases, synergistic effects are obtained, i.e. theactivity of the mixture is greater than the activity of the individualcomponents.

[0185] Suitable components of the mixture are, for example, thefollowing compounds:

[0186] Fungicides

[0187] aldimorph, ampropylfos, ampropylfos potassium, andoprim,anilazine, azaconazole, azoxystrobin,

[0188] benalaxyl, benodanil, benomyl, benzarnacril,benzamacryl-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate,

[0189] calcium polysulphide, capsimycin, captafol, captan, carbendazim,carboxin, carvon, chinomethionate (quinomethionate), chlobenthiazone,chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate,clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuiram,

[0190] debacarb, dichlorophen, diclobutrazol, diclofluanid, diclomezine,diclorane, diethofen-carb, difenoconazole, dimethirimol, dimethomorph,diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,ditalimfos, dithianon, dodemorph, dodine, drazoxolon,

[0191] ediphenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,

[0192] famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide,fluquinconazole, flurprimidol, flusilazol, flusulfarnide, flutolanil,flutriafol, folpet, fosetyl aluminium, fosetyl sodium, fthalide,fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole,furconazol-cis, furmecyclox,

[0193] guazatine,

[0194] hexachlorobenzene, hexaconazole, hymexazol,

[0195] imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),iprodione, irumamycin, isoprothiolane, isovaledione,

[0196] kasugamycin, kresoxime-methyl, Copper formulations, such as:copper hydroxide, copper naphthenate, copper oxychloride, coppersulphate, copper oxide, oxine-copper and Bordeaux mixture,

[0197] mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,metalaxyl, metconazol, methasulfocarb, methfuroxam, metiram, metomeclam,metsulfovax, mildiomycin, myclobutanil, myclozolin,

[0198] nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

[0199] ofurace, oxadixyl, oxamnocarb, oxolinicacide, oxycarboxim,oxyfenthiine,

[0200] paclobutrazol, pefurazoate, penconazole, pencycuron, phosdiphen,pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,procymidon, propanocarb, propanosine sodium, propiconazole, propineb,pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

[0201] quinconazole, quintozene (PCNB),

[0202] Sulphur and sulphur formulatons,

[0203] tebuconazole, tecloflalam, tecnazene, tetcyclacis, tetraconazole,thiabendazol, thicyofen, thifluzamide, thiophanate-methyl, thiram,tioxymid, tollofos-methyl, tolylfluanid, triadimefon, triadimenol,triazbutil, triazoxide, trichiamide, tricyclazole, tridemorph,triflumizole, triforine, triticonazol,

[0204] uniconazole,

[0205] validamycin A, vinclozolin, viniconazole,

[0206] zarilamid, zineb, ziram and

[0207] Dagger G,

[0208] OK-8705,

[0209] OK-8801,

[0210] α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,

[0211]α-(2,4-dichlorophenyl)-β-fluoro-b-propyl-1H-1,2,4-triazole-1-ethanol,

[0212]α-(2,4-dichlorophenyl)-β-methoxy-a-methyl-1H-1,2,4-triazole-1-ethanol,

[0213]α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,

[0214](5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,

[0215] (E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,

[0216]1-isopropyl{2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate

[0217] 1-(2,4-dichlorophenyl)-2-(1 H-1,2,4-triazol-1-yl)-ethanone-O-(phenylmethyl)-oxime,

[0218] 1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,

[0219] 1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,

[0220] 1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,

[0221]1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,

[0222]1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,

[0223]1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,

[0224] 1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol,

[0225] 2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,

[0226]2,2-dichloro-N-[1-(4-chlorophenyl)-ethlyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,

[0227] 2,6-dichloro-5-(methylthio)-4-pyrimidinyl thiocyanate,

[0228] 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,

[0229] 2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,

[0230] 2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,

[0231]2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,

[0232]2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-a-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,

[0233] 2-amrinobutane,

[0234] 2-bromo-2-(bromomethyl)-pentanedinitrile,

[0235]2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,

[0236]2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatornethyl)-acetamide,

[0237] 2-phenylphenol(OPP),

[0238] 3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,

[0239]3,5-dichloro-N-[cyan[(1-methyl-2-propynyl)-oxy]-methyl]-benzanide,

[0240] 3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,

[0241] 3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,

[0242]4-chloro-2-cyan-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,

[0243] 4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,

[0244]8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,

[0245] 8-hydroxyquinoline sulphate,

[0246] 9H-xanthene-9-carboxylic acid2-[(phenylamino)-carbonyl]-hydrazide,

[0247]bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,

[0248] cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,

[0249]cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,

[0250] ethyl [(4-chlorophenyl)-azo]-cyanoacetate,

[0251] potassium bicarbonate,

[0252] methanetetrathiol sodiun salt,

[0253] methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,

[0254] methylN-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,

[0255] methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

[0256] N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexancarboxamide.

[0257]N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,

[0258]N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,

[0259] N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzolsulplionamide,

[0260] N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,

[0261] N-(4-hexylphlenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,

[0262]N-(5-chloro-2-niethylphenyl)-2-metlioxy-N-(2-oxo-3-oxazolidinyl)-aceturnide,

[0263] N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,

[0264] N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,

[0265]N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N′-methoxy-methaneimidoamide,

[0266] N-forrnyl-N-hydroxy-DL-alanine sodium salt,

[0267]O,O-diethyl-[2-(dipropylamino)-2-oxoethyl]-ethylphosphorwnidothioate,

[0268] O-methyl S-phenyl phenylpropylphosphoramidothioate,

[0269] S-methyl 1,2,3-benzothiadiazole-7-carbothioate,

[0270] spiro[2H]-1-benzopyran-2,1′(3′H)-isobenzofuran]-3′-one,

[0271] Bactericides

[0272] bronopol, dichlorophen, nitrapyrin, nickeldimethyldithiocarbatnate, kasugarnycin, octhilinone, flirancarboxylicacid, oxytetracycline, probenazole, streptomycin, tecloflalam, coppersulphate und other copper formulations.

[0273] Insecticides/Acaracides/Nematicides

[0274] abamectin, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin,

[0275] bacillus thuringiensis,4-Bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoro-methyl)-1H-pyrrole-3-carbonitrile,bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC,brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim,butylpyridaben,

[0276] cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan,cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos,N-[(6-chloro-3-pyridinyl)-methyl]-N′-cyano-N-methyl-ethaneimidoamide,chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine,cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyromazine,

[0277] deltamethrin, demeton M, demeton S, demeton-S-methyl,diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos,dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos,dioxathion, disulphoton,

[0278] edifenphos, emamectin, esfen valcrate, ethiofencarb, ethion,ethofenprox, ethoprophos, etrimphos,

[0279] fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad,fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, fluazuron,flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate,fonophos, formothion, fosthiazate, fubfenprox, furathiocarb,

[0280] HCH, heptenophos, hexaflumuron, hexythiazox,

[0281] imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb,isoxathion, ivermectin, lamda-cyhalothrin, lufenuron,

[0282] malathion, mecarbam, mevinphos, mesulphenphos, metaldehyde,methacrifos, methamidophos, methidathion, methiocarb, methomyl,metolcarb, milbemectin, monocrotophos, moxidectin,

[0283] naled, NC 184, nitenpyram

[0284] omethoate, oxamyl, oxydemethon M, oxydeprofos,

[0285] parathion A, parathion M, permethrin, phenthoate, phorate,phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,pirimiphos A, profenophos, promecarb, propaphos, propoxur, prothiophos,prothoate, pymetrozine, pyrachlophos, pyridaphenthion, pyresmethrin,pyrethrum, pyridaben, pyrimidifen, pyriproxifen,

[0286] quinalphos,

[0287] salithion, sebufos, silafluofen, sulphotep, sulprofos,

[0288] tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron,tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox,thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin,tralomethrin, triarathene, triazophos, triazuron, trichlorfon,triflumuron, trimethacarb,

[0289] vamidothion, XMC, xylylcarb, zetamethrin.

[0290] A mixture with other known active substances, such as herbicides,or with fertilizers and growth regulators, is also possible.

[0291] The active substances can be used as such, in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders,dusting agents and granules. They are used in a customary manner, forexample by pouring, spraying, atomizing, broadcasting, dusting, foamapplication, brushing, etc. It is also possible to apply the activesubstances by the Ultra-Low-Volume method or to inject the activesubstance formulation or the active substance itself into the soil. Theseed of the plants may also be treated.

[0292] When the active substances according to the invention are used asfungicides, the application rate may be varied within a relatively largerange, depending on the method of application. In the treatment of plantparts, the application rates of active substance are in general between0.1 and 10,000 g/ha, preferably between 10 and 1000 g/ha. In thetreatment of seed, the application rates of active substance are ingeneral between 0.001 and 50 g per kilogram of seed, preferably between0.01 and 10 g per kilogram of seed. In the treatment of the soil, theapplication rates of active substance are in general between 0.1 and10,000 g/ha, preferably between 1 and 5000 g/ha.

[0293] The compositions used for protecting technical materials containthe active substances in general in an amount of 1 to 95%, preferably of10 to 75%.

[0294] The use concentrations of the active substances according to theinvention depend on the type and occurrence of the microorganisms to becontrolled and on the composition of the material to be protected. Theoptimal amount for use can be determined by test series. In general, theuse concentrations are in the range from 0.001 to 5% by weight,preferably from 0.05 to 1.0% by weight, based on the material to beprotected.

[0295] The activity and the action spectrum of the active substances tobe used according to the invention in material protection or of thecompositions, concentrates or very generally formulations which can beprepared therefrom can be increased if optionally further antimicrobialcompounds, fungicides, bactericides, herbicides, insecticides or otheractive substances are added for increasing the action spectrum orachieving special effects, such as, for example, additional protectionfrom insects. These mixtures may have a broader action spectrum than thecompounds according to the invention.

[0296] Even when used against animal pests, the substances according tothe invention may be present as a mixture with synergistic agents incommercial formulations and in the use forms prepared from theseformulations. Synergistic agents are compounds by means of which theaction of the active substances is increased without the addedsynergistic agent itself having to be actively effective.

[0297] The active substance content of the use forms prepared from thecommercial formulations may vary within wide ranges. The activesubstance concentration of the use forms may be from 0.0000001 to 95% byweight of active substance, preferably between 0.0001 and 1% by weight.

[0298] Application is effected in a customary manner adapted to one ofthe use forms.

[0299] The preparation and use of substances according to the inventionare illustrated by the following examples.

PREPARATION EXAMPLES Example 1

[0300]

[0301] 1.4 g (10 mmol) of potassium carbonate are added to a solution of1.7 g (7 mmol) of 2,5-dibromo-4-methyl-1H-imidazole in 40 ml ofacetonitrile at room temperature. The mixture is stirred for 10 minutesat room temperature, and 1.7 g (7 mmol) of2-methyl-5-nitro-benzenesulphonyl chloride are then added. Stirring iscarried out for a further 20 hours at room temperature and the reactionmixture is then poured onto 100 ml of water. The mixture formed isextracted twice with 50 ml of diethylether in each case. The combinedorganic phases are dried over sodium sulphate and then evaporated downunder reduced pressure. The remaining residue is chromatographed onsilica gel using methylene chloride as mobile phase. 1.6 g (51% oftheory) of1-(2-methyl-4-nitro-benzenesulphonyl)-2,4-dibromo-5-methyl-1H-imidazoleare obtained in this manner in the form of a colourless solid substanceof melting point 187 to 189° C.

[0302] The substances shown in Table 8 below are also prepared by theabovementioned methods. TABLE 8 (I)

Exa mple No.

X Melting point (° C.) 2

—CN 195-200 3

Cl 223-227 (1:1 Isomer mixture) 4

Cl 176-180 (4:5 Isomer mixture) 5

—CN 180-183 6

—CN ¹H-NMR-Spectrum (CDCl₃, TMS): δ = 2.66 (s, 3H, CH₃), 7.55 (s, 2H,arom. prot.); 7.62 (d, 1H, J =8.4 Hz, arom. prot.); 7.71 (s, 1H, arom.prot.); 8.49 (d, 1H, J =8.4 Hz, arom. prot.); 9.12 (s, 1H, arom. prot.)ppm 7

Br 66-72 8

Br 130-136

Use Examples Example A

[0303] Phytophthora Test (Tomatoes)/Protective

[0304] Solvent: 47 parts by weight of acetone

[0305] Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

[0306] For the preparation of an expedient formulation of activesubstance, 1 part by weight of active substance is mixed with the statedamount of solvent and emulsifier and the concentrate is diluted to thedesired concentration with water.

[0307] To test for protective activity, young plants are sprayed withthe formulation of active substance at the stated application rate.After the spray coating has dried on, the plants are inoculated with anaqueous spore suspension of phytophthora infestans. The plants are thenplaced in an incubation cabin at about 20° C. and 100% relativehumidity.

[0308] The evaluation is carried out 3 days after the inoculation. 0%means an efficiency which corresponds to that of the control, while anefficiency of 100% means that no attack is observed.

[0309] Active substances, application rates and test results are shownin the table below. TABLE A Phytophthora Test (tomatoes)/protectiveApplication rate of active substance Efficiency Active substance in g/hain % According to the invention

50 99

50 96

50 96 Disclosed in EP-A 0 238 824:

50 85

50 71

Example B

[0310] Plasmopora Test (Grapevines)/Protective

[0311] Solvent: 47 parts by weight of acetone

[0312] Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

[0313] For the preparation of an expedient formulation of activesubstance, 1 part by weight of active substance is mixed with the statedamounts of solvent and emulsifier, and the concentrate is diluted to thedesired concentration with water.

[0314] To test for protective activity, young plants are sprayed withthe formulation of active substance at the stated application rate.After the spray coating has dried on, the plants are inoculated with anaqueous spore suspension of Plasmopara viticola and then remain for 1day in an incubation cabinet at about 20° C. and 100% relative humidity.The plants are then placed in a greenhouse for 5 days at about 21° C.and about 90% relative humidity. The plants are then moistened and areplaced in an incubation cabinet for 1 day.

[0315] The evaluation is carried out 6 days after the inoculation. 0%means an efficiency which corresponds to that of the control, while anefficiency of 100% means that no attack is observed.

[0316] Active substances, application rates and test results are shownin the table below. TABLE B Plasmopara test (grapevines)/protectiveApplication rate of active substance in Efficiency Active substance g/hain % According to the invention

50 92

50 93

Example C

[0317] Phaedon Larvae Test

[0318] Solvent: 7 parts by weight of dimethylformamide

[0319] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0320] For the preparation of an expedient formulation of activesubstance, 1 part by weight of active substance is mixed with the statedamounts of solvent and emulsifier, and the concentrate is diluted to thedesired concentration with water.

[0321] Cabbage leaves (Brassica oleracea) are treated by immersion inthe formulation of active substance of the desired concentration andinfested with larvae of the horseradish beetle (Phaedon cochleariae) aslong as the leaves are still moist.

[0322] After the desired time, the kill in % is determined. 100% meansthat all beetle larvae were killed; 0% means that no beetle larvae werekilled.

[0323] Active substances, application rates and test results are shownin the table below. TABLE C plant-damaging insects Phaedon larvae testActive sub- stance concen- tration in Kill Active substances % by weightin % after 7 d According to the invention

0.1 100

0.1 100

Example D

[0324] Plutella Test

[0325] Solvent: 7 parts by weight of dimethylformamide

[0326] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0327] For the preparation of an expedient formulation of activesubstance, 1 part by weight of active substance is mixed with the statedamounts of solvent and emulsifier, and the concentrate is diluted to thedesired concentration with water.

[0328] Cabbage leaves (Brassica oleracea) are treated by immersion inthe formulation of active substance of the desired concentration andinfested with caterpillars of the diamondback moth (Plutella xylostella)as long as the leaves are still moist.

[0329] After the desired time, the kill in % is determined. 100% meansthat all caterpillars were killed; 0% means that no caterpillars werekilled.

[0330] Active substances, application rates and test results are shownin the table below. TABLE D plant-damaging insects Plutella test Activesub- stance con- centration in Kill in Active substances % by weight %after 7 d According to the invention

0.1 100

0.1 100

Table E

[0331] Material Protection Test

[0332] To demonstrate the activity against fungi, the minimum inhibitoryconcentrations (MIC values) of compounds according to the invention aredetermined.

[0333] Active substances according to the invention are added, inconcentrations of 0.1 mg/l to 5000 mg/l to an agar which is preparedusing malt extract. Solidification of the agar is followed bycontamination with pure cultures of test organisms. After storage fortwo weeks at 27° C. and 60 to 70% relative humidity, the minimuminhibitory concentration (MIC value) is determined. The MIC valuecharacterizes the lowest concentration of active substance at whichthere is no growth at all of the microbe species used.

[0334] Active substances, test organisms and MIC values are shown in thetable below. TABLE E Material protection test Minimum inhibitoryconcentration (MIC value) in mg/l Active substance according to ExampleNo. Test organism 2 5 Penicillium brevicaule 100 100 Chaetomium globosum100 100 Aspergillus niger 200 200

1. Nitrophenyl-sulphonyl-imidazoles of the formula

in which a) X represents cyano, R¹ represents halogen, alkyl or phenyl,R² represents halogen, alkyl or phenyl, R¹ and R², together with thecarbon atoms to which they are bonded, represent an optionallysubstituted benzene ring or represent an optionally substitutedheterocyclic ring and R³ represents halogen, alkyl or phenyl or b) Xrepresents halogen, R¹ represents halogen, alkyl or phenyl, R²represents halogen, alkyl or phenyl, R¹ and R², together with the carbonatoms to which they are bonded, represent an optionally substitutedheterocyclic ring or R¹ and R², together represent a doubly bondedradical of the formula

 and R³ represents halogen, alkyl or phenyl, 2.Nitrophenyl-sulphonyl-imidazoles of the formula (I) according to claim1, in which x represents cyano, R¹ represents fluorine, chlorine,bromine, straight-chain or branched alkyl having 1 to 6 carbon atoms orphenyl, R² represents fluorine, chlorine, bromine, straight-chain orbranched alkyl having 1 to 6 carbon atoms or phenyl, or R¹ and R²,together with the carbon atoms to which they are bonded, represent abenzene ring which may be monosubstituted to trisubstituted, identicallyor differently, by halogen, cyano, nitro, formyl, carbamoyl,thiocarbamoy; alkyl, alkoxy, alkylthio or alkylsulphonyl, each having 1to 5 carbon atoms; halogenalkyl, halogenalkoxy, halogenalkylthio orhalogenalkyl-sulphonyl, each having 1 to 4 carbon atoms and 1 to 5identical or different halogen atoms; halogenoalkenyl orhalogenoalkenyloxy, each of which is straight chain or branched and eachof which has 2 to 4 carbon atoms and 1 to 5 identical or differenthalogen atoms; alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl,alkylsulphonyloxy, hydroximinoalkyl, alkoximinoalkyl orcyanimino(alkoxy)alkyl, each having 1 to 4 carbon atoms in theindividual alkyl moieties; cycloalkyl having 3 to 6 carbon atoms;phenyl, phenoxy, phenylthio, pyridyl, pyridyloxy and/or pyridylthio, itbeing possible for each of these radicals to be monosubstituted ordisubstituted, identically or differently, by halogen, cyano, nitro,alkyl having 1 to 4 carbon atoms and/or halogenalkyl having 1 to 4carbon atoms and 1 to 5 identical or different halogen atoms, or R¹ andR², together with the carbon atoms to which they are bonded, represent abenzene ring which is substituted by doubly linked alkylene having 3 or4 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms, it beingpossible for the alkylene or dioxyalkylene groups to be monosubstitutedto tetrasubstituted, identically or differently, by halogen, alkylhaving 1 to 4 carbon atoms and/or halogenoalkyl having 1 or 2 carbonatoms and 1 to 5 identical or different halogen atoms, or R¹ and R²,together with the carbon atoms to which they are bonded, represent a 5-or 6-membered heterocyclic ring which contains one, two or threeidentical or different heteroatoms and may be monosubstituted totrisubstituted, identically or differently, by halogen, cyano, nitro,hydroxyl, amino, formyl, carboxyl, carbamoyl, thiocarbamoyl, alkylhaving 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms,halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1to 5 identical or different halogen atoms, alkoxycarbonyl having 1 to 4carbon atoms in the alkoxy moiety, cycloalkyl having 3 to 6 carbonatoms, halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkylsulphonyl having 1 to4 carbon atoms and 1 to 5 identical or different halogen atoms,alkylamino having 1 to 4 carbon atoms, hydroxyalkylamino having 1 to 4carbon atoms, dialkylamino having 1 to 4 carbon atoms in each alkylgroup, alkylcarbonyl having 1 to 4 carbon atoms in the alkyl moiety,hydroximinoalkyl having 1 to 4 carbon atoms in the alkyl moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, alkylcarbonyloxy having 1 to 4carbon atoms In the alkyl moiety and/or halogenoalkylcarbonyloxy having1 to 4 carbon atoms in the halogenoalkyl group and 1 to 5 identical ordifferent halogen atoms, the oxygen atoms not being adjacent where theheterocyclic ring contains more than one oxygen atom, and R³ representsfluorine, chlorine, bromine, straight-chain or branched alkyl having 1to 6 carbon atoms or phenyl.
 3. Nitrophenyl-sulphonyl-imidazoles of theformula (I) according to claim 1, in which x represents fluorine,chlorine or bromine, R¹ represents fluorine, chlorine, bromine,straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl,R² represents fluorine, chlorine, bromine, straight-chain or branchedalkyl having 1 to 6 carbon atoms or phenyl, or R¹ and R², together withthe carbon atones to which they are bonded, represent a 5- or 6-memberedheterocyclic ring which contains one, two or three identical ordifferent heteroatoms, such as oxygen, sulphur and/or nitrogen, and maybe monosubstituted to trisubstituted, identically or differently, byhalogen, cyano, nitro, hydroxyl, amino, formyl, carboxyl, carbamoyl,thiocarbamoyl, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 to 4carbon atoms and 1 to 5 identical or different halogen atoms,alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,cycloalkyl having 3 to 6 carbon atoms, halogenoalkylsulphinyl having 1to 4 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5 identicalor different halogen atoms, alkylamino having 1 to 4 carbon atoms,hydroxyalkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4carbon atoms in each alkyl group, alkylcarbonyl having 1 to 4 carbonatoms in the alkyl moiety, hydroximinoalkyl having 1 to 4 carbon atomsin the alkyl moiety, alkoximinoalkyl having 1 to 4 carbon atoms in thealkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety,alkylcarbonyloxy having 1 to 4 carbon atoms in the alkyl moiety and/orhalogenoalkylcarbonyloxy having 1 to 4 carbon atoms in the halogenoalkylgroup and 1 to 5 identical or different halogen atoms, the oxygen atomsnot being adjacent where the heterocyclic ring contains more than oneoxygen atom, or R¹ and R² together represent a doubly bonded radical ofthe formula

 and R³ represents fluorine, chlorine, bromine, straight-chain orbranched alkyl having 1 to 6 carbon atoms or phenyl. Process for thepreparation of nitrophenyl-sulphonyl-imidazoles of the formula (I)according to claim 1, characterized in that imidazole derivatives of theformula

 in which R¹, R² and X have the abovementioned meanings, are reactedwith nitrobenzene-sulphonyl nalides of the formula

 in which R³ has the abovementioned meaning and Hal represents chlorineor bromine, optionally in the presence of an acid acceptor andoptionally in the presence of a diluent,
 5. Composition for controllingvegetable and animal pests, characterized by a content of at least onenitrophenyl-sulphonyl-imidazole of the formula (I) according to claim 1.6. Use of nitrophenyl-sulphonyl-imidazoles of the formula (I) accordingto claim 1 for controlling vegetable and animal pests.
 7. Method forcontrolling vegetable and animal pests, characterized in thatnitropheny-sulphonyl-imidazoles of the formula (I) according to claim 1are applied to the pests and/or their habitat
 8. Process for thepreparation of compositions for controlling vegetable and animal pest,characterized in that nitrophenyl-sulphonyl-imidazoles of the formula(I) according to claim 1 are mixed with extenders and/or surfactants.